Deep sea mining system

ABSTRACT

A system for recovering minerals, mineral ores and their compounds from the bottom of the sea and other deep water areas which employs a sled-like unit having a reaction chamber with an open bottom adapted to be dragged along the ocean floor while the reaction chamber is supplied with solvents and/or reagents which will react with the minerals and/or ores and other mineral bearing materials desired to be recovered and means associated with the reaction chamber for collecting the desired materials in more concentrated form and for bringing them to the surface which includes subjecting mixtures of the desired materials and waste to electrical deposition and/or chemical segregation. In one form of the apparatus employed the desired materials on the ocean floor are treated with chemical solvents and reagents which will react with the minerals and/or the compounds sought and mixtures of the solution and reaction products with some waste forming material are brought to the surface for extraction of the desired products by electrolytic deposition and segregation in a surface unit.

United States Patent [1 1 Wanzenberg et al.

[451 Feb. 25, 1975 -DEEP SEA MINING SYSTEM [76] Inventors: FrederickWheelock Wanzenberg;

Fritz' Walter Wanzenberg, both of 9 Campbell in, Larchmont, NY. 10538[22] Filed: Oct. 12, 1970 [21] Appl. No: 80,015

Related US. Application Data [60] Division of Ser. No. 700,470, Jan. 25,1968, Pat. No. 3,748,248, which is a continuation-in-part of Ser. No.526,970, Feb. 10, 1966, abandoned.

[52] US. Cl 204/109, 204/105, 204/111 [51] Int. Cl. C22d 1/12, C22d 1/02[58] Field of Search 299/5, 8; 166/.6; 204/105-107, l49152, 206-211,]08,109,110

[56] References Cited UNITED STATES PATENTS 532,183 1/1895 Pike 299/8565,342 8/1896 Frasch 299/5 X 738,758 9/1903 Baxeres de Alzugaray 75/101989,802 4/1911 Rennie 204/109 X 1,394,147 10/1921 204/13 2,144,7431/1939 299/8 2,900,320 8/1959 Metcalfe et a1 204/300 EC 3,063,921ll/l962 Leibowitz 204/110 3,474,015 10/1969 Norris 204/151 FOREIGNPATENTS OR APPLICATIONS 6,937 3/1907 Great Britain 204/12 PrimaryExaminer-F. C. Edmundson Attorney, Agent, or Firm-Guy A. Greenawalt [57]ABSTRACT A system for recovering minerals, mineral ores and theircompounds from the bottom of the sea and other deep water areas whichemploys a sled-like unit having a reaction chamber with an open bottomadapted to be dragged along the ocean floor while the reaction chamberis supplied with solvents and/or reagents which will react with theminerals and/0r ores and other mineral bearing materials desired to berecovered and means associated with the reaction chamber for collectingthe desired materials in more concentrated form and for bringing them tothe surface which includes subjecting mixtures of the desired materialsand waste to electrical deposition and/or chemical segregation. In oneform of the apparatus employed the desired materials on the ocean floorare treated with chemical solvents and reagents which will react withthe minerals and/or the compounds sought and mixtures of the solutionand reaction products with some waste forming material are brought tothe surface for extraction of the desired products by electrolyticdeposition and segregation in a surface unit.

17 Claims, 13 Drawing Figures PAIENTEUrms ms 3.868.131 2 sum 1 OF 5INVENTORS FREDERICK WHEELOCK WANZENBERG DEEP SEA MINING SYSTEM Thisapplication is a division of application Ser. No. 700,470, filed Jan.25, 1968 now U.S. Pat. 3,748,248, which is a continuation-in-part ofapplication Ser. No. 526,970, filed Feb. 10, 1966, now abandoned.

This invention relates to mining and is more particu- 'larly concernedwith a unique system for recovering metals and minerals from oceans,lakes or rivers which employs solution chemistry, solvent extraction andelectro-deposition, with the recovered materials being in the form ofcathode deposits, electro separated granules or slimes which are removedto the surface for further processing;

Conventional methods employed heretofore for collecting minerals, insoluble and insoluble state, from bodies of water have generallyinvolved dredging, draglines and bucket conveyors which are suitable foroperations in shallow water areas only. No satisfactory methods havebeen developed for the commercial recovery of metals and minerals fromreasonable to great depths. Most proposed methods have been found eitheruneconomical or impractical for recovering deeply deposited metals ortheir chemical compounds.

The principal object of the present invention is the provision of asystem for mining in deep water locations which is economical andpractical, wherein extraction of valuble metallic ions or fractionsthereof is accomplished at the bottom of the sea or the floor of a lakeor stream, by solution chemistry and solvent extraction and theisolation of the most valuable portions of mineral compounds byelectrodeposition or electrosegregation so as to render them readilyremovable to the surface, thereby eliminating the need for moving gangueas well as the valuable fractions, and other cost incurring operationsincident to normal dressing, smelting and refining operations.

It is another object of the invention to provide a method and anapparatus whereby valuable metals are concentrated and converted fromthe ore to cathodic or anodic particles or solution ions at the bottomof the sea or beneath other deep bodies of water so as to facilitateremoval to the surface for final processing.

Another object of the invention is to provide a mining system whereinsolvents such as acids, bases, cyanides, fluorides, silico-fluorides,acid-sulphate solutions, alkalines, stannates, fluoborate solutions,pyrophosphates, amine-complex solutions, etc., singly or in combinationare added to mineral bearing nodules and ores at the bottom of the oceanor other bodies of water so as to permit ionization of the non-metallicand metallic materials trapped therein and enable the same to be readilybrought to the surface.

It is a further object of the invention to provide an apparatus forrecovery of minerals from the ocean floor which involves applying apotential between a fixed grid anode at or below the bottom surface anda fixed or replaceable cathode in juxtaposition near the anode in theenvironment of dissolved or ionized metallic or mineral compounds, witha solvent feeding mechanism which can be part of an electro-depositionmechanism all of which may be either stationary or movable after themanner of a sled, the cathode being in the form of sheets, coils, barsor strips which may be transported to the surface whenelectro-deposition is completed, and with the necessary electricalcurrent supplied from a ship, a buoy or other surface installation.

A still further objectof this invention is the use of closed circuittelevision to properly place stationary rigs or to guide mobile rigs inseeking the most productive sites or locations for mining.

Another object of the invention is to provide an apparatus forelectro-deposition of ore particles which include traveling belts on asled-like frame which may be arranged so that both anode andcathodedeposits may be obtained if desired.

It is still a further object of the invention, in one form thereof, toprovide an apparatus on the bottom of the ocean for crushing nodules andore particles and mixing these particles with leeching solutions, acidsand reagents on the ocean floor so that the solutes formed, or thedissolved or precipitated products of reaction, liberated gases, finesolids, etc. may then be removed to the surface where the valuableminerals can be extracted by electro-deposition, solvent extraction,mineral dressing and other conventional processing.

These and other objects and advantages of the invention will be apparentfrom a consideration of the method and apparatus which is shown by wayof illustration in the accompanying drawings wherein:

FIG. 1 is a perspective view, largely schematic. showing a system orapparatus for recovering minerals by electro-deposition from the bottomof the ocean;

FIG. 2 is a perspective view of a system or apparatus for mineralrecovery by electro-deposition from the ocean floor wherein the systemis mobile;

FIG. 2A is a longitudinal section taken on the line 2a2a of FIG. 2, to asmaller scale with parts shown schematically;

FIG. 2B is a longitudinal section similar to FIG. 2a showing a modifiedform of the apparatus;

FIG. 3 is a perspective view of a mobile system for the recovery ofminerals from the ocean floor by solution chemistry and employingelectro-deposition at the surface;

. FIG. 4 is a perspective view showing the bottom of the ocean recoveryunit of FIG. 3 connected to a surface unit employing solution chemistry,electrodeposition, and electro-segregation for the recovery of minerals;

FIG. 5 is a longitudinal cross section taken on line 55 of FIG. 4, to anenlarged scale, and with portions broken away; I

FIG. 6 is a fragmentary section showing a portion of FIG. 5 to a largerscale;

FIG. 7 is a fragmentary cross section showing a portion of FIG. 28 to alarger scale;

FIGS. 8 and 8A are fragmentary sections showing electrical contactdetails;

FIG. 9 is an exploded perspective with portions cut away showing anoreion separation unit; and

FIG. 10 is a fragmentary section showing a modification of the ore-ionseparation unit of FIG. 9.

Referring first to FIG. 1, there is illustrated schematically a systemfor collecting ore particles from the bottom of the ocean byelectro-deposition which embodies a collecting apparatus adapted to bemoved to intervals along the ocean floor. The apparatus comprises aboxlike member 1 forming an ionization or electrolyte receiving chamber2, the member 1 having insulated sides which enclose an electrolyte (notshown) comprising both reagents and products of reaction for dissolvingthe metallic compounds found on or underneath the ocean floor. The openbottom of the member l which is adapted to be positioned on the oceanfloor coated stainless'steel, are mounted at the top of one side of thechamber 2 so that they may be unrolled across th'e'top of the chamber 2and form cathodes for permanent deposition of ore fractions. As theportions of the coils 4 and 5 disposed over the electrolyte accumulatedeposits, the free ends of the strip portions are pulled out unrollingthe coils 4 and 5 and exposing fresh surfaces over the electrolytechamber 2.

A probe 6 is employed with the chamber 2 which may be inserted into thedeep ocean subfloor to the depth of the ore body, ballistically or bydrilling and which serves to feed reagents into the subfloor. A tubemember 7 forming a rifle-barrel. is used to guide the probe 6 in anattitude perpendicular to the ocean bottom and to provide a tower orsupporting structure for mounting a television camera 8 and associatedlight 8'. A breech block 9 is provided on the upper end of thetowerwhich carries a charge to fire the center probe 6 into theoceanbottom. The breech block 9 is connected to buoy 10 by umbilicalcord 11 which contains electrical power lines, television cables,control and instrumentation cables, strain member, conduit for thereagents, etcJThe umbilical cord 11 leads from the service buoy 10 whichcontains reagent supplies power generators, .direct reading andrecording instruments,

fuel supply, television monitor, etc. A manhole cover 12 permits accessto and servicing of the equipment in the buoy 10. A generator air intakeand ventilator 13 permits the intake of air but not of water and anexhaust pipe 14 is provided for the electrical generator. Bungs 15, 16,17 etc. are provided for replenishing oil, fuel, reagents and dyes. Alarge number of similar buoys may be serviced by a single ship.

The free ends 18, 18' of the metal coils or strips 4 and 5 are attachedby a harness 19 to an anchoring weight 20 which is in turn connected bycable 21 to a buoy 22 to mark the position of the coil ends 18, 18'. Aharness 23 isattached to the box member 1 to enable the apparatus to belowered and retrieved with an anchor 24 and spar buoy 25 which serve toestablish and mark the end of the harness cable. 7

The bottom grid 13 is flexible or comprises fore and aft connectedstrips so as to accomodate irregularities in the ocean floor and is of astable metal, for example, stainless steel, plastic reinforced carbonrods, plated copper, platinum or palladium, or of graphite, and formsone of the electrodes in the plating or electrolysis sub-system. Thegrid 3 constitutes an anode which is set at a polarity positive to thatof the coils or strips 4 and 5 which constitute cathodes and both anodicand ca thodic materials may be recovered. The anodic materials supportthe system chemically and the cathodic products are the metals which arerecovered. Anodic materials and elements such as chlorine, bromine,iodine, etc. are used as chemical reagents to produce soluble metalsalts and may also be recovered commer-' cially. Cathodic materials and,elemental metals which are deposited as well as their salts, acids,bases, oxides and hydrides, due to chemical action at the cathodicsurfaces constitute the useful output.

A modified form of apparatus is shown in' FIG. 2 which incorporates acollecting unit adapted to be towed so that it is dragged along theocean floor. The

collecting unit 25 comprises a box-like frame 26 having an open bottomin which there is a grid 27. The box is divided into two connectingionization or electrolyte chambers 28 by a longitudinal partition 29 inconjunction with front and rear hingedly mounted aprons 30 and 31 whichhelp retain the electrolyte and reduce loss of the latter to thesurrounding water. Two pairs of traveling belts 32, 32 and 33, 33' aresupported on drums or rollers 34 and 34' (FIG. 2A) journaled at oppositeends of the frame 26 and the belt supporting rollers 34 at the trailingend of the frame are driven by toothed wheels or discs 35, the shafts ofwhich are connected to the roller shafts by reversing or planetarygears. indicated at 36 in FIG. 2A. The. teeth on the spur wheels diginto the ocean floor as the frame 26 is advanced and the wheels arecaused to rotate and drive the belts 32, 32' and 33, 33' so that thebottom runs thereof advance in the direction of advance of the frame'26.

The chambers 28 are supplied with reagents which are stored in pressureequalized bags 37 and fed to each chamber 28 via feeder lines 38 and39'having control valves 40 and 41. The valves 40 and 41 automaticallycontrol the rate of reagent feed depending upon preselected ionizationrate pH or conductivity of the electrolyte. The chambers 28 containinsoluble ores, reagents, the products of reaction, gases and solutionsas electrolytes (including freshv or sea water) in which are dissolvedthe normally insoluble mineral compounds which through chemical reactionor electrolysis become ions and hence are platable or separable.

The belts 32, 32' and 33, 33 which are of conducting plastic, conductingrubber, graphite or inhibitor-coated metal, pass through a collectingchamber 42 arranged at the forward end of the frame 26 and materialdeposited on the surfaces of the belts will be brushed off into thecollecting chamber 42 by a brush 43 supported on a shaft journaled inthe side walls of the chamber 42 and having a connecting drive,indicated at 44, with the shaft of the belt supporting rollers 34'. Thebrush 43 may also serve to add graphite which has been lost and to workit into the surfaces of the moving belts. Suction in the collectingchamber 42 is created by gas intrusion from the decomposition of waterin the electrolysis unit 45, by gas injection from the surface (atshallow depths), by gases liberated at the cathode belts or frame suchas hydrogen, by gases liberated at the anode belts or frame such aschlorine and/or oxygen, by suction pumps at the water surface, etc. Thesuction in the collecting chamber 42 will be applied to a narrow areathe entire width of the belt chamber 28 by suctionscraper element 46 viapipes 47. A flexible hose v48 connects the collection chamber 42 to thesaddle coupling 49 which connects to the conduit 50 running to thesurface.

An alternate construction of the apparatus of FIG. 2 is shown in FIG.2B. In this arrangement of the belts 32, 32' and 33, 33 of the apparatusof FIG. 2 are replaced by an equal number of porous, non-conducting,continuous belts 60, which serve as'filters to keep ore particles outand also as repositories for soluble and insoluble materials forrecovery, and an equal number of cathodes 61 are disposed between theupper and lower runs of the belts and spaced above the bottom anode gridstructure 62. Soluble minerals (ions) while in the confines of the belts60 react to form insoluble precipitates, some gain electrons to becomeelemental metals.

some are displaced by cathodic ions to become elemental metals or theyare plated out on the surface of the cathodes 61 to become elementalmetals. The insoluble materials for recovery include the foregoingsoluble materials made insoluble as described plus insoluble materialsfrom previous actions. The belts 60 convey the soluble materials whichhave been made insoluble and the insoluble materials from previousactions forward to suction scraper elements 63 and 64 corresponding toelement 46 of FIG. 2, which remove the same from the top and bottomsides of the lower run of the belt. Similar suction-scraper elements 65and 66 are disposed at the opposite end of the unit for removing thematerials from the belts after the latter have passed over the top sideof the cathodes 61. The cath- "odes 61 are provided with a series ofvertical passageways 67 so as to transmit soluble materials (ions) tothe top side and permit maximum use of the cathode surfaces. Feederpipes 68 connect the suction-scraper elements 63, 64, 65 and 66 with acommon conduit 69 or if electro-segregation is employed eachbelt-cathode combination will have the suction-scraper elements whichare operative thereon connected to separate conduits for collection ofthe particles. The anode grid 62 is made of passive material, forexample, carbon, platinum or palladium, usually having a commonreference potential of zero volts. The cathodes 61 are made of carbon,iron or stainless steel, though materials such as copper may be usedwhere copper molecules will go into solution as copper ions to displacesolution ions of more noble metals which will plate out to replace. the

ionized copper molecule. The unit is otherwise constructed asillustrated in FIGS. 2 and 2A.

A further modification of the system is illustrated in FIG. 3 where thefunctions of retrieval and electrodeposition are separated, that is, anocean floor unit 70 is provided which prepares and retrieves the oreparti- .cles and dissolved minerals while separation of the valuableelements is accomplished later at the waters surface by theelectro-segregation and electrodeposition units shown in FIGS. 4 to 10.Physical beneficiation, i.e., separation by metal types, is alsoaccomplished in the surface units.

The retrieval unit 70 comprises a box-like housing forming frame7l, withan open bottom and runners 72, which is adapted to be pulled along theocean floor like a sled. A wide mesh screen 73 at the'forward end of theframe 71 will pass ore lying on the ocean floor to a hinged apron 74 andinto a reagent or solvent mixing compartment or chamber 75. A scoop-likescraper 76 is mounted in the chamber 75 in front of a pair ofcrushing-grinding belts 77, 78 which are mounted on pairs of end rollers79, 80 and 79', 80. The belt supporting rollers are mounted on shaftsjournaled in the side walls of the frame 71 and are differentiallydriven by suitable drive connections with a motor reducer indicated at81. Reagents are fed into the mixing chamber 75 through holes 82 in thescraper 76 and conduit 83 which leads to a surface supply source. Thecrushing-grinding belts 77, 78 empty into a collection chamber 84 at therearward end of the frame 71 and the materials, which continue to reactor dissolve in the presence of the reagents and/or solvents as they passbetween the belts 77 and 78, are drawn into a motor driven suction pump85 and then into a cyclone 86.

bon dioxide and chlorine in most operations. In the,

The cyclone 86 separates the tine, dissolved, precipitated and freeparticles, solutes and entrained and chemically generated gases whichflow upwards into umbilical cord-like conduit 87 to the surface. Thelarger particles and ga'ngue whichenter the down-flow of cyclone 86 maybe discharged at the apex to the ocean floor or raised to the surfacethrough conduit 88. When it is desired to recover large and smallparticles and solutes (with gases) one of the conduits can beeliminated. The conduit column will be light due to the liberation ofgases by chemical reaction, which will consist largely of hydrogen,oxygen, nitrous oxide, carevent the conduit column is not light enough,water decomposition, by electrolysis, surface suction pumps, air fromthe surface etc., may be used to lighten the same and to obtain thedesired velocity of the material transported in the conduit.

In those situations were the product to be recovered is such that one ormore chemical reactions are desirable or requiredv before optimumsolubility or ionization can be realized, the proper reagents are usedsequentially, or in combination as complex solvent reagents, dependingupon their stability when mixed or when they are jointly in contact withthe ore. Inhibitors may also be required to prevent unwanted reactionsand the use of suitable catalysts is contemplated to speed up ionizationand improve electro-deposition rates. These reagents and/or solvents,inhibitors and catalysts may be applied at the bottom surface or underthe ocean floor to the depthof the ore seam, with or without apersistent tracer which will identify depleted or mined areas so thatthey are not re mined.

Referring to FIG. 4 of the drawings, an ocean floor recovery unit'70,which is constructed as illustrated in FIG. 3, is shown coupled to asurface unit 90, the unit providing for chemical treatment, crushing andgrinding of ore and the unit 90 providing for conversion of the materialreceived from unit 70 into elemental metals, metal salts and bases,oxides, and hydrides by electro-deposition and electro-segregation ofthe metals into specific metals or groups of metals and their respectivecompounds.

Referring particularly to FIGS. 5 and 6, the surface unit 90 comprises agenerally rectangular tank-like housing 91 which is divided, as shown inFIG. 5, into two main chambers or compartments 92 and 93 and endchambers or compartments 94 and 95. The materials from the unit 70enterthe intake chamber 94 from either or both conduits 87 and 88 asshown in FIG. 5 and continue down into chamber 94 to sprocket member 96at the bottom of the chamber 94 which opens into subchamber 97 inthe'bottom portion of the left (as viewed in FIG. 5) main chamber 92.The sprocket member 96 is motor driven and forms an end support for anopen meshed plastic belt 98. The belt 98 extends horizontally .in thesub-chamber 97 to an end support roller 100 and serves to transportheavy mass materials by movement of the bottom run to the right in FIG.5 while movement of the top run stirs liquids and fines to the left. Thenet movement of the heavy input materials will be from the left anodesub-chamber 97 to the right anode sub-chamber 101 through the opening102 between a hinged gate 103 and the base or bottom structure 104 tothe sub-chamber 101 in the bottom portion of or below the right mainchamber 93. An open meshed'plastic belt 105 of the same character asbelt 98 is supported in the horizontal sub-chamber 101 on motor drivensprocket roller 107 and co-operating end .opening 102 and gate 103. Thebelt 105 is driven in the same direction as belt 98, the bottom runtransporting heavy, material to the right while the top run stirsliquids and fines to the left. The heavy materials, such as sand, shellsand solid gangue, is discharged as waste at the bottom of the endchamber 95 through a discharge pipe 110 by a driven screw 111, which maybe of plastic or rubber composition. Thefines and liquids rise in thechamber 95 and pass through valve 112 to outlet conduit 113. The conduit113 may discharge these materials as waste or the reagents therein maybe recovered, by concentration, and recycled so as to be used again.Where desired the materials may be neutralized before disposal so as toavoid water pollution. v

The flow of the ore and other materials recovered by the recovery unit70 and delivered to the ion-ore separation unit 90 is through chambersor passageways providing a path or configuration resembling a U-tube. Toprovide for positive pressure on the materials entering the unit 90reservoir 114 is provided at the top end of the chamber 94 whichconstitutes the upstream riser and reservoir 115 is provided at the topend of the chamber 95 which constitutes the downstream riser. Thereservoirs 114 and 115 compensate for surge and cause little change inhead which makes for efficient operation. A valve 116 and outlet conduit117 are provided opposite the inlet conduit 88 for use in cleaning thesystem or removing obstructions, enabling clean water to be forced intothe inlet from conduit 88 andthrough the outlet 117 to draw solids andliquids from theend chamber 94. Also, samples for assay purposes may beobtained in this manner to determine whether the large particles in thedown-flow of the cyclone 86 t are to be accepted into the unit 90 orrejected.

Since the materials delivered to the ion-ore separation unit 90 have arelatively high percentage of solids, water receiving and heatingchambers or headers 120 and 121 are provided in the bottom structure 104of the unit below each of the sub-chambers 97 and 105 with inlets 122and 123 for sea, river or lake water. Suitable electrical heatingelements 124 and 125 are provided in the chambers 120 and 121 withcurrent supplied. through terminals indicated at 126. The heated waterpasses throughtaperedholes. 127 in the anode member 128, which separatesthe sub-chamber 97 from the heating chamber 120, and into the left anodechamber where, together with anodic gases and other products formed, itwill mix with the input ore,

' reacting with-the ore, ore derivatives and reagents carried up fromthe ocean bottom unit 70. Soluble positive ions, which are indicated bynumerals 129 in FIG. 6, and which are formed by chemical reaction in theunits 90 and 97 pass upwardly' in the sub-chamber 97 through the meshbelt 98 and are attracted by cathodes 130 until stopped by unglazed claytubes 131 which enclose the cathodes 130. The clay tubes 131, which arepreferably fabricated of flowerpot grade (red) clay, and which serve asbarriers, permit the passage of electrons and'small positive ions, suchas hydrogen, but prevent the passage of large positive ions, such ascopper. The principal function of the clay tubes 131 is to separate thepositive metal ions from their ore and gangue environment. The positivemetal ions will adhere to the surfaces of the tubes 131 which arerotated and carry the ions around and upwards between the .8 tubesurfaces and the flexiblelower flanges 132, preferably formed of Nylon,on the I beams 133 which are disposed in parallel spaced relationbetween the clay tubes 130. The rotation of the tubes will drive themetal ions upwardly between the I beams 133 into the interspaces ofnon-conducting fiber or cloth conveyor belt 134 to a second cathodeforming member 137 which is disposed between lower and upper runs of thebelt 134, the latter being mounted on end support rollers 138 and 138'having their shafts journaled in the side walls of the housing 91 anddriven by connection with a common drivemechanism for the apparatuswhich is indicated at 140 in FIG. 4. Some fine ore and gangue (141 inFIG. 6)-will be carried around and up between the clay tubes 130 and thebottom flanges 132 of the I beams 1-33 but these comprise particleswhich are electrically neutral and they do not move up, except by chanceor convection current, and generally will pass through holes 142 in the[beam webs and will be carried down and into the subchamber 97 again bythe downwardrotation of the clay tubes 130 as illustrated in FIG. 6 Theelectrically neutral ore and gangue particles serve to force the lips ofthe flexible bottom flanges 132 of the I beams 133 away from thesurfaces of the tubes 130, as they move down between the same, causingopenings upward for migration of the ions. The top and bottom flanges ofthe I beams 133 are of Nylon plastic or other resilient material havinggood insulation and wear characteristics and are proportioned so as tobe spread apart during assembly with resultant continuous pressureon thetubes 130 by the I beam flanges 132. Extrusions of Nylon or similarresilient material 143 and 144 at opposite ends of the subchamber 97complete the separating structure between the cathode compartment orchamber 92 and the anode compartment or sub-chamber 97. The member 144between the left and right hand anode subchambers 97 and 101 has holes145 for the passage of ions and/or gangue from the left to right handchamber. Additional traveling belts 146, 147, 148 separated by a seriesof cathode forming members. 150, 151,. 152, 153, 154, are arranged invertically stacked or pile forming relation above the lowermost belt 134and the associated cathode member 137, thebelts being of the samecharacter, and supported and driven in the same manner, as belt 134 andthe cathode forming members being arranged between the belt runs, asshown in FIG. 5, and having vertical passageways 156 for passage of themetal ions upwardly in the cathode chamber. A like arrangement isprovided in the right hand anode chamber or sub-chamber 101 and in thecathode chamber 93 above the same. The end extrusion 157, at the exitend of sub-chamber 101, (FIG 5) is provided with holes for passage ofmaterial from the sub-chamber 101 to the vertical end-chamber 95. A vent158 in the subchamber 97 traps and collects anodic gases and dischargesthem to outlet 159. I

The cathodes are made of graphite unless it is desired to use cathodicmetal to displace metals from the solution which are loweron thehydrogen activities series '(more noble) than the cathode metal used. Inthe apparesin, which is an insulator, and extend above the level of thehighest cathode members with cover members or lids 160 and 161 eachsealed with O-ring gaskets so that the water level can extend above theseal. Vents 162 and 163 are provided to bleed off gases such ashydrogen, chlorine and oxygen formed in the process.

The materials collected on the traveling belts 134, etc., are removed bysuction-scraper units, indicated at 165, 166, 167 and 168 in FIG. 5,which are the same character as units 65 and 66 of FIGS. 2 and 7 anddraw off the materials trapped on the belt surfaces in the same manner.The suction-scraper units 165 etc. have connections with suction pipesor conduits 170 which convey water and insoluble metal compounds andelemental metals to settling tanks for collection and refining. Thenumberof electrodes and the number of separate pipes 170 which areemployed will determine the degree of separation of the materials intotheir respective metal groups.

Since ion travel is slow, a magnetic field is created by electricalcoils, indicated at 171, which are incorporated in the wall structuresor wrapped around the electrolytic tanks 92, 93, 94 and 95 inhorizontal, helix fashion and fed current through suitable connectingmeans from a supply line. The coils create strong magnetic fields havingvertical lines of force which speed up the movement of the ions. In thedesign of the apparatus the distances through which the ions must travelmay be held to a minimum. For example, the distance from the anodes 128to the clay barrier tubes may be as little as mm., the barrier tubes maybe as little as 2 cm. in diameter and the belts 134, etc. can be aslittle as /2 mm. thick. The cathodes can be kept thin so that positiveions migrating through the holes 156 will travel minimum distances.

Freedom of movement of the unit 90 is necessary and good electricalcontact must be maintained. Therefore, special electrical connectors 172(FIGS. 4, 8 and 8A) are provided for the anode and cathode members,which are mounted on the outside walls of the electrolyte tanks. Asshown in FIGS. 8 and-8A, a graphite plug 173 is slidably mounted inbushing 174 set in the tank wall 175 with O-rings to affect sealing. Thebushing 174 is secured by nut 176 which also secures the chamber end ofa dust bellows 177. The outer end of the bellows 177 is secured to asocket joint member 178 on the outer end of the plug.173 which serves asthe electrical contact for a connecting rod and terminal member 180,which is in turn connected to the electrical cable 181. Engagement ofthe plug 173 against the end wall of the cathode member, 137 forexample, is maintained by a spring 182 which operates between the balland pin 183 to provide in co-operation with hinged bracket member 184,an overcenter lock, for holding the connector in the contact-makingposition of FIG. 8 or the noncontact position of FIG. 8A.

Referring to FIG. 9, electrical contact is made with cathode member 130by means of graphite pillow blocks 185 and 186, which are springmounted, with the base pillow block 186 having outside electricalcontact through graphite pin 187 pressed into pillow member 186 andfixedly mounted through wall 175.

As shown in FIG. 9, the drive for rotating the cathode forming members130 comprises pinions 190 which are caused to rotate in the samedirection by idlers 191. The pinions 190 may be connected to the claybarrier tubes 131 only to or both the tubes 131 and the cathodes 130.The pinions 190 form part of the drive mechanism 140 (FIG. 4). When thecathodes 130 are rotated they are designed in cross-section like a fourleaf clover so that the voltage influence upon positive ions will bevery slowly a pulsating one. When the cathodes are not rotated thevoltage can be rotated" by commutation. The cathodes 130 are hollow andone end is open for receiving sea water which is distributed throughopenings to the chambers formed between the cathodes and the clay pipeswhere sodium will react with water to form sodium hydroxide and theresulting mixture will pass through tubes 192 and connecting ldtub 1,

A modification of the ion-ore separation unit is shown in FIG. 10 inwhich there are fixed or. stationary cathodes 195 in clay wedges 196between the rotating drums 197, the latter being insulators orconductors, for example, conducting rubber, with the potential, whenconductors, being more positive than the fixed cathodes 195.

In using the apparatus the cathodes 130 at the bottom of the stack orpile in the cathode chamber 92 would be set at a potential, for example,10 to 20 volts more negative than the anodes 128. The cathode 137 whichis the next higher in the pile would be set at 2 to 4 volts morenegative than the cathode 130 and the next cathode would be set at 3 to6 volts more negative than cathode 137. A typical arrangement'would beto provide voltages of 0, 20, 24, 29, -35 and 42 for the anode 128 andthe first to the fifth cathodes 130, 137, 150, 151, 152, respectively.The right cathode chamber is set up in the same manner. This arrangementis made in view of known characteristics of metals and their compounds,base metals requiring relatively little inducement to go into solutionas ions and the noble metals exhibiting much greater reluctance to gointo solution from their elemental state or from insoluble compoundstate and requiring higher voltage and- /or oxidizing chemical reactionsto convert the metal atoms or molecules into (soluble) metal ions.Consequently, the low voltage electrodes will reduce the more noblemetal ions to their elemental state and the higher voltage electrodeswill reduce the base metal ions to their elemental state. With thearrangement referred to, positive ions will migrate upwards from theanode chamber and through the cathode pile. The first cathode 130 isemployed to separate the ions from the ore and gangue and not fordeposit of positive ions. The secondcathode 137 will take most noblemetals out of solution, converting ions to atoms or molecules, such as,to oxides or hydroxides, the third cathode will take out the less noblemetals and so forth until the last cathode will deposit on theassociated belt the base metals, 1

such as zinc, aluminum, magnesium, etc., which will react with Na+OI I-to form hydroxides. The various components involved in a typicaloperation are illustrated schematically in FIGS. 6, 7 and 10. Insolublemetal compounds are indicated at 200. Reactive negative ions resultingfrom chemical and electrolytic action are indicated at 201. Anodicallyoxidizing reactive negative ions are indicated at 202 and anodicallyoxidized molecules at 203. Soluble positive metal ions sought areindicated at I29. Nascent. dissolving, metal compounds are indicated at205. Negative metal ions displaced from insoluble metal compounds 200are indicated at 206. Also. reactive negative ions resulting fromelectrolytic and chemical actions .are indicated at 207. Insoluble metalcompounds produced by reaction of 129 and 207 are indicated at 208.Insoluble ore and gangue particles 11 are indicated at 141. The cathode150 is fabricated of a displaceable metal which is ionized into cathodeatoms indicated by 210. Typical actions and reactions are: the reactingof insoluble metal compounds 200 with reactive negative ions 201 to formsoluble positive metal ions 129 which are sought, as indicated at 211;the reacting of insoluble metal compounds 200 with reactive anodicallyoxidized molecules 203 to form soluble positive metal ions 129 asindicated at 212; reactive negative ions 201 oxidizing (loss ofelectrons) to form anodically oxidized atoms 202 which combine to formanodically oxidized molecules 203, as indicated at 213; soluble positivemetal ions 129 reduced (gain electrons) to elemental atoms or molecules209, as indicated at 214; soluble positive metal ions 129 reacting withreactive negative ions 201, 206, 207 to form insoluble metal compounds208, as indicated at 215; insoluble cathode metal atoms from cathode 150displacing soluble metal ions 129 from solution, the atoms from 150,shown as 210, oxidizing to soluble ions by giving up electrons topositive metal ions 129 and the latter being reduced to elemental metalatoms or molecules 209, i.e., are plated out as indicated at 216; andsoluble positive ions 129 reducing (gaining electrons) to elementalmetal molecules or atoms 209, i.e., are plated out as indicated at 217%m- Oxidation occurs at the anodes and reduction occurs at the cathodes.Free negative ions are reduced to chlorine, oxygen, nitrous oxide,sulphur dioxide, carbon dioxide, et c., many of which result from theaction of reagents on insoluble sea bottom ore. Many of these will reactwith insoluble metal compounds and form a few insoluble ores withcertain metals, notably silver and mercury. Two cathode chambers areemployed in the apparatus so that conditions are made most favorable fortwo main groups of metals.

Most metal chlorates are soluble in water. Metal benzoates, metalnitrates and metal sulphates generally, are soluble in water. Metalchlorides, except for silver, mercury and chromium are soluble in water.Metal bromides of the metals desired are soluble in water. Only aninsignificant number of metal oxides are soluble in water. The mostinteresting metal carbonates, with the exception of chromium, andthemost interesting metal hydroxides, with the exception of auric hydroxideare insoluble in water. Metal silicates generally and metal iodides withthe exception of nickel, tin and zinc are insoluble in water. In theillustrated apparatus the left chamber 92 is designed to first dissolve(or receive dissolved) and then precipitate by electro-deposition andits concomitant chemical reduction all metals, but very little silverand mercury. The right chamber 93, when 'supplied with fresh water andsmall amounts of sodium hydroxide and ammonia as conveyor fluid isdisigned to extract silver and mercury and their compounds, most othermetals having been removed in the left chamber 92. Fresh water andammonium hydroxide enters the header 121 via pipe 123 and rises to thefirst cathode through the right anode chamber 101 (FIGS. and 9) in theright chamber 93 and with dissolved sodium ,hydroxide from both left andright chambers proceeds upwardly through the ion-ore separtion units130', 131 etc. into the cathode stack. The leeched gangue is returned tothe right anode chamber 101 and the positive metal ions and liquidscontinue upwardly through the cathode stack where the elemental metals,indicated at .0 n F GS Qandfi an metal p ds, 8 are moved from the beltsby suction-scraper units 165', 166, 167", 168 and carried with entrainedfluids through conduits 170. The negative voltages increase from cathodeto cathode as in the left cathode chamber 92 so that the more noblemetals plate out at the lower cathodes and the more base metals plateout at the upper cathodes resulting in electro-segregation by metaltypes.

Tests have shown efficient extraction of all metals except the alkaliand alkaline earth groups. Employing the instant process the apparatuscollects the ores, converts insoluble ore to soluble metal ions andreduces these ions to their elemental or simple compound forms,segregating them by metal type groupings ready for refining into metalbillets or products. A large part of the metal yield comes about throughthe chemical reduction of the metal ions. A large part of the yieldresults in insoluble metal oxides and hydroxides formed at the cathodesurfaces due to the generation of reactive alkali metal hydroxides atthese surfaces. The hydroxide reaction at the cathodes results in allmetals below magnesium in the hydrogen activities series forminginsoluble hydroxides (or insoluble oxides). All other metal ions 129react with the hydroxide ions 207 of sodium hydroxide say, to forminsoluble hydroxides or oxides, designated 208 in FIG. 6. The same typeof reaction occurs with sodium carbonate and certain silicates, iodidesetc., which are soluble in the cathode chambers and react with metalions to make them insoluble. Correspondingly, to convert insoluble metalores into soluble ions requires that these ores be converted tochlorates, bromides, some iodides, benzoates, nitrates, sulphates ormost chlorides, which is accomplished in the sea bottom unit and/or inthe anode chambers of the surface units, with some reactions occurringin ean-95am.

Silver forms a special case as the carbonate and chloride are relativelyinsoluble in water. Addition of ammonium hydroxide into the head 121with fresh water, rather than salt water, permits them to become solublesince high chlorine ion content in the fluid forces silver ions out ofsolution; Reaction of the silver ion in the cathode chamber is thenidentical to that for other metals- . reaction also occurring at thecathode resultsfrom the effect of abundant nascent and molecularhydrogen which reduces some metal compounds to their elemental metalsand reacts with some metals and compounds to form transient hydrideswhich are in the form of gas or solids which readily decompose. Thiseffect is not harmful and aids in providing more elemental metals 209from compounds 208. Both elemental and nascent hydrogen will reduce somemetal ions 129 to elemental metals 209, both with, and independently of,the other reactions already cited. Because of high adsorption ofhydrogen by platinum and palladium, their use as cathode material isparticularly applicable to catalyze these reactions.

Tests with apparatus having cathodes that are free of electricalconnections, except the first, 130, the second 137 optionally and thelast cathode have shown good metal and metal compound recovery. Thevoltage of these floating cathodes is then established by their positionin the voltage drop gradient through the electrolyte between theconnected cathodes controlled in addition by the reduction activity ateach floating cathode surface so as to be self-regulating with regard tozone positive ion concentrations the electrolyte.

Tests also indicate the highest metal and metal compound recoveryresults when employing low anode efficiency (high gas formation at theanodes) and high cathode efficiency (low gas formation at the cathodes).

We claim:

1. A method for recovering metals and metal compounds from materialwhich has been collected from mineral deposit areas formed under waterwhich comprises separating from the collected material desirable mineralbearing ore materials so as to segregate said mineral bearing orematerials from sand, shells and other undesired waste material,discarding the undesired waste material, treating the separated mineralbearing ore material in a processing area including oxidizing insolublemetal compounds in said material to convert the same to soluble metalions and radicals, separating the resultant products from the gangue andcollecting and removing by electrolysis the resultant products to obtainthe desired metals and/or metal compounds.

2-. A method as set out in claim 1 wherein an electrolyte is employedwhich, at least in part,corresponds to sea water and wherein theoxidized products are processed in an electrolytic separating apparatushaving a plurality of electrodes which are supplied with differentelectrical potentials so as to plate out separate metals or groups ofmetals simultaneously.

3. The process of conditioning sea water slurry including insolubleprecious metal compounds for subsequent derivation of precious metalvalues therefrom,

which comprises a. introducing the slurry into the anode chamber of anelectrolysis vessel,

b. partially isolating said slurry from the cathode chamber of saidvessel, and

c. establishing a current flow between the anode and cathode chambers,

d. said current flow being sufficient to at least partially decomposethe solubilize said precious metal compounds.

4. The process of claim 3, further characterized by said sea watermixture comprising a slurry of sea water and bottom sediment fines.

5. The process of claim 4, further characterized by said bottom sedimentfines comprising siliceous-based bottom sediment material.

6. The process of claim 3, further characterized by Said e water tur .nud .t1l1 .fi Plant Parts;

7. The process of deriving precious metal values from sea watermixtures, containing precious metal complexes, which comprises a.electrolytically treating the sea water mixtures in the anode chamber ofelectrolysis vessel to at least partially decompose said precious metalcomplexes, and

b. deriving precious metal compound precipitates from theelectrolytically treated mixtures,

c. said deriving step including the reaction of decomposed preciousmetal complexes with a precipitating agent to form insoluble preciousmetal salts,

d. separating and treating the insoluble precious metal salts to deriveprecious metal values.

8. The process of claim 7, further characterized by a. the sea watermixtures comprising slurries of sea water and bottom fines,

b. said slurry being derived by disturbing the sea bottom sediments andwithdrawing sea wat er an i entrained sediment fines from the area ofdisturbance.

9. The process of claim 8, further characterized by the electrolyticallytreated slurry being subjected to oxidizing conditions to biochemicallycondition the slurry for enhancement of the efficiency of extraction ofthe precious metal values.

10. The process of claim 7, further characterized by said sea watermixtures comprising slurries of sea water, siliceous-based bottomsediment fines, and halophytic plant parts.

11. A process for extracting metal values from sea water which comprisesa. withdrawing from the sea bottom area a portion of sea bottom sedimentfines as a slurry in sea water,

b. treating the slurry to break down the metal compounds in thesediments and thereby to enrich the sea water in such values, and

c. thereafter separating the water from the sediments and extracting themetal values from the water,

(1. said treating step including the electrolysis of said slurry in ananode chamber of an electrolytic cell.

12. The process of claim 11, further characterized by said bottomsediment fines forming siliceous based materials.

13. The process of extracting precious metal values from sea watermixtures containing precious metal compounds, which comprises a.introducing said sea water into the anode chamber of an electrolysisvessel,

b. partially isolating said mixture from the cathode chamber of saidvessel,

c. establishing a current flow between the anode and cathode chambers toat least partially decompose the metal compounds,

d. introducing the electrolytically treated sea water into aprecipitation vessel,

e. reacting the decomposed metal compounds with a precipitating agent toform insoluble salts of the precious metals,

f. treating said insoluble salts to als in elemental form.

14. The process of claim 13, whereinsaid treating step includes thesteps of a. dissolving said insoluble salts in a dilute solution ofhydrochloric acid and an oxidizing agent, and

b. separating the dissolved salts from accompanying insoluble compounds.

15. The process of deriving precious metal values from sea watermixtures containing precious metal compounds which comprises a. exposingsaid sea water mixture to electrolytic oxidizing conditions tosolubilize said precious metal compounds,

b. reacting the oxidized precious metal compounds with a precipitatingagent to form insoluble precious metal salts, and

c. treating said precious metal salts to obtain elemental preciousmetals.

16. The process of claim 15, wherein chlorine gas is bubbled throughsaid dilute HCl solution containing dissolved precious metal salts.

17. The process of claim 3, further including the steps of oxidizingsaid sea water mixture to further decompose and solubilize said preciousmetal compounds.

derive precious met-

1. A METHOD FOR RECOVERING METAL AND METAL COMPOUNDS FROM MATERIAL WHICHHAS BEEN COLLECTED FROM MINERAL DEPOSIT AREAS FORMED UNDER WATER WHICHCOMPRISES SEPARATING FROM THE COLLECTED MATERIAL DESIRABLE MINERALBEARING ORE MATERIAL SO AS TO SEGREGATE SAID MINERAL BEARING OREMATERIALS FROM SAND, SHELLS AND OTHER UNDESIRED WASTE MATERIAL,DISCARDING THE UNDESIRED WASTE MATERIAL, TREATING THE SEPARATED MINERLBAARING ORE MATERIAL IN A PROCESSING AREA INCLUDING OXIDIZING INSOLUBLEMETAL COMPOUNDS IN SAID MATERIAL TO CONVERT THE SAME TO SOLUBLE METALIONS AND RADICALS, SEPARARING THE RESULTANT PRODUCTS FROM THE GANGUE ANDCOLLECTING AND REMOVING BY ELECTROLYSIS THE RESULTANT PRODUCTS TO OBTAINTHE DESIRED METALS AND/OR METAL COMPOUNDS.
 2. A method as set out inclaim 1 wherein an electrolyte is employed which, at least in part,corresponds to sea water and wherein the oxidized products are processedin an electrolytic separating apparatus having a plurality of electrodeswhich are supplied with different electrical potentials so as to plateout separate metals or groups of metals simultaneously.
 3. The processof conditioning sea water slurry including insoluble precious metalcompounds for subsequent derivation of precious metal values therefrom,which comprises a. introducing the slurry into the anode chamber of anelectrolysis vessel, b. partially isolating said slurry from the cathodechamber of said vessel, and c. establishing a current flow between theanode and cathode chambers, d. said current flow being sufficient to atleast partially decompose the solubilize said precious metal compounds.4. The process of claim 3, further characterized by said sea watermixture comprising a slurry of sea water and bottom sediment fines. 5.The process of claim 4, further characterized by said bottom sedimentfines comprising siliceous-based bottom sediment material.
 6. Theprocess of claim 3, further characterized by said sea water mixtureincluding halophytic plant parts.
 7. The process of deriving preciousmetal values from sea water mixtures, containing precious metalcomplexes, which comprises a. electrolytically treating the sea watermixtures in the anode chamber of electrolysis vessel to at leastpartially decompose said precious metal complexes, and b. derivingprecious metal compound precipitates from the electrolytically treatedmixtures, c. said deriving step including the reaction of decomposedprecious metal complexes with a precipitating agent to form insolubleprecious metal salts, d. separating and treating the insoluble preciousmetal salts to derive precious metal values.
 8. The process of claim 7,further characterized by a. the sea water mixtures comprising slurriesof sea water and bottom fines, b. said slurry being derived bydisturbing the sea bottom sediments and withdrawing sea water andentrained sediment fines from the area of disturbance.
 9. The process ofclaim 8, further characterized by the electrolytically treated slurrybeing subjected to oxidizing conditions to biochemically condition theslurry for enhancement of the efficiency of extraction of the preciousmetal values.
 10. The process of claim 7, further characterized by saidsea water mixtures comprising slurries of sea water, siliceous-basedbottom sediment fines, and halophytic plant parts.
 11. A process forextracting metal values from sea water which comprises a. withdrawingfrom the sea bottom area a portion of sea bottom sediment fines as aslurry in sea water, b. treating the slurry to break down the metalcompounds in the sediments and thereby to enrich the sea water in suchvalues, and c. thereafter separating the water from the sediments andextracting the metal values from the water, d. said treating stepincluding the electrolysis of said slurry in an anode chamber of anelectrolytic cell.
 12. The process of claim 11, further characterized bysaid bottom sediment fines forming siliceous based materials.
 13. Theprocess of extracting precious metal values from sea water mixturescontaining precious metal compounds, which comprises a. introducing saidsea water into the anode chamber of an electrolysis vessel, b. partiallyisolating said mixture from the cathode chamber of said vessel, c.establishing a current flow between the anode and cathode chambers to atleast partially decompose the metal compounds, d. introducing theelectrolytically treated sea water into a precipitation vessel, e.reacting the decomposed metal compounds with a precipitating agent toform insoluble salts of the precious metals, f. treating said insolublesalts to derive precious metals in elemental form.
 14. The process ofclaim 13, wherein said treating step includes the steps of a. dissolvingsaid insoluble salts in a dilute solution of hydrochloric acid and anoxidizing agent, and b. separating the dissolved salts from accompanyinginsoluble compounds.
 15. The process of deriving precious metal valuesfrom sea water mixtures containing precious metal compounds whichcomprises a. exposing said sea water mixture to electrolytic oxidizingconditions to solubilize said precious metal compounds, b. reacting theoxidized precious metal compounds with a precipitating agent to forminsoluble precious metal salts, and c. treating said precious metalsalts to obtain elemental precious metals.
 16. The process of claim 15,wherein chlorine gas is bubbled through said dilute HCl solutioncontaining dissolved precious metal salts.
 17. The process of claim 3,further including the steps of oxidizing said sea water mixture tofurther decompose and solubilize said precious metal compounds.